In the zero-field-cooled exchange bias (ZEB) effect the unidirectional magnetic anisotropy is set at low temperatures even when the system is cooled in the absence of external magnetic field. La1.5Sr0.5CoMnO6 stands out as presenting the largest ZEB reported so far, while for La1.5Ca0.5CoMnO6 the exchange bias field (HEB) is one order of magnitude smaller. Here we show that La1.5Ba0.5CoMnO6 also exhibits a pronounced shift of its magnetic hysteresis loop, with intermediate HEB value in respect to Ca-and Sr-doped samples. In order to figure out the microscopic mechanisms responsible for this phenomena, these compounds were investigated by means of synchrotron X-ray powder diffraction, Raman spectroscopy, muon spin rotation and relaxation, AC and DC magnetization, X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The parent compound La2CoMnO6 was also studied for comparison, as a reference of a non-ZEB material. Our results show that the Ba-, Ca-and Sr-doped samples present a small amount of phase segregation, and that the ZEB effect is strongly correlated to the system's structure. We also observed that mixed valence states Co 2+ /Co 3+ and Mn 4+ /Mn 3+ are already present at the La2CoMnO6 parent compound, and that Ba 2+ /Ca 2+ /Sr 2+ partial substitution at La 3+ site leads to a large increase of Co average valence, with a subtle augmentation of Mn formal valence. Estimates of the Co and Mn valences from the L-edge XAS indicate the presence of oxygen vacancies in all samples (0.05≤ δ ≤0.1). Our XMCD results show a great decrease of Co moment for the doped compounds, and indicate that the shift of the hysteresis curves for these samples is related to uncompensated antiferromagnetic coupling between Co and Mn. arXiv:1909.05287v1 [cond-mat.mtrl-sci]

Four compositions of Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-delta) were studied for phase, oxygen uptake-release, and transition metal (TM) oxidation states after solid state processing and with in situ heating from 300 to 1273 K in air. X-Ray diffraction showed that all compositions except one had the cubic perovskite structure at all temperatures; that with x, y = 0.2 was a mixture as prepared, becoming predominantly cubic at high temperature. Thermogravimetry showed a reversible oxygen absorption-desorption of approximately +/-1% from 700 to 1273 K. X-Ray absorption and Mössbauer spectroscopy showed a majority TM(3+) valence, with at most 40% TM(4+). Up to a temperature of 1073 K, the TM(4+) was reduced to TM(3+). Further heating of the composition with x, y = 0.2 to 1233 K resulted in the reduction of Co(3+) to Co(2+). Results from room temperature measurements confirm the thermally activated carrier hopping mechanism with charge fluctuations, while the high temperature delocalized carrier conductivity occurs with a small amount of TM reduction and without phase change for the initially cubic samples.

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57 Fe Mössbauer spectra of Fe 3 O 2 BO 3 reveal a combined effect of charge ordering and electron delocalization between 112 and 450 K. On the basis of the temperature dependence of the isomer shifts and quadrupole interactions, together with the information from previously obtained transport data, we are able to discuss the arrangement of Fe 2+ and Fe 3+ in the structure and the dynamics of the electronic configurations. We found a charge-delocalization transition around 300 K. Below this temperature, formation of pairs of Fe ions with mixed valence takes place in part of the crystalline structure.

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